Process for preparing phenylene-diamine derivatives



PateniedAug. 1,1945 v r 2,381,015

raocsss roa ram-ammo puma nnarva'nvas IIaroldVenBramer-andLeeGDavL l Dofl. Tenn, assl nors toEastmanKodakOompany.' Rochester, N. Y.,- a corporation oi New Jersey mv mamas m, 1, 194:. Serial No. man

12 Claims. (CI. 26.4")

'lhisinvmtionrelatestoaprocessi'orpreparthe proportions of oxidusetforth abovavla ins and more parl:10:i molar proportions, are preferred, other l-lmilarly to a process for preparing N,N'-dialkylproportions can he used. The amount of catalyst p-phenylenediaminq wherein the alkyl lroupa used is advantageously from about 0.5 per cent eanheallkeordlfl'erent toahout percent or the weight otthe mixture In the oopending application of Harold Von or N-alkyl-p-nitroaniline and carbonyl comlramer, Lee 0: Davy and Milton L Clemens, Jr., pound. I Serial No, 304.504, med November 0, 1940 (now The molar ratio of carbonyl compound to 8- United Btatslatent 2,823,048, dated July 13, albl-p-nitroaniline is advantaaeously more than lmLithas hesnshown thatsymmetrical N,N'-V 10 2:1, and is preferably between about 2:1 and dlalhhp-phenyl can be prepared in about 10:1. The temperature employed is adsoody'leldsbyhydmeenatingamixtureoi'p- 'vaniageoualybetweenabout 100C.'andabout allllxtureotall-alhl p-nitroanilineand an aide- 170' C. The hydrog n pressure employed is adhyde ketone vantageously between about 1000 and 1500 poundper square inch. The reaction mass is preferably vlzorously asitated during the hydrogenation. UsualLv the hvdrogenations are complete in from 6 to 10 hours.

m by When the hydrogenations are complete, the can prepared eood fi l reaction masses are filtered to remove the cam a Illllture of a liealkyl-p-llltroanlline and an lyst andthen vacuum distilled at pressures from IIdehydeom-hetoneJnthepresenceoi'acatabst 0.1to0.2mrn.otmercury.

essentially copper oxide, chromium The following examples will serve to illustrate caldeand bariumozida'nie N.N'-dlalkyl-pournewpmcess.

obtainable!oui'newproc- Y I sample 1.N,N -di-(|ec0ndary butyl) 42-pin:- :sscanbe isolatedina suml llyl ylenediamine It is. locordlnglman object o! our-invention to 194- s. (1 mole) of N-secondary butyl-p-nitroprovideanewprocesslor preparing NJW-dialblanillnewere dissolved in 144 g. (2 moles) ct II-pheny Other objects will become methvlethyl ketone and. p ed n a Steel y apparent hereinafter lenating autoclave. 27 g. 01 catalyst co In accordance with our invention, we hydroof an lntermlzture of copper oxide, chromium senate a mixture at a N-alkyl-p-nitroanmm and oxide and barium oxide were added to the soloa carbonyl compound selected from the grou tion. The autoclave wassealed and the reaction mass heated to a temperature of 165 C. Hydro- :en was introduced until the pressure was 1500 poundsper square inch. The reaction mass was aeitated. for fl hhours under these conditions, alter which the temperature was allowed to tell to The pressure on the autocla s-was released and the reaction mass was filtered to remove the catalyst The filtered reaction mass was'heated to distill ofl excess meth- IIethyI ketone. The residue was then distilled under Vacuum, 210.3 g. of N,N-dl-(secondary butyl) -p-phenylenediamine boiling at to N0 v I v talned. Thisquantityrepreeentedayieldoiflli einetahentopreventa-risein percent. 4g.oimateria;lremainedinihestill Thelowerthetun-i potarresidue.

mm or the meme, mm on: mammlenedamim I 104 g. (1 mole) oil-secondary butyl-p-nitromum. aniline weredlloiv'edin 1 Ir (manholes) a! C. at 0.1 to 0.2 mm. of mercurypressure were obialltothatcttheroom. The.

masswasniteredto'reethyl ketone.

- methyl ter iary butyl methvl amyl I tively minted with aredirom' processcan are not "sultablein practicing our process.

' ployed'in the above examples can cataly copper oxide, chromium The autoclave was then sealed and the reaction mass was heated to 185' C.

Hydrosen was introduced until the pressure rose inch. The reaction agitated under these conditions after which time the temperature was allowed to was then and the reaction move the catalyst. The filtered mass was heated to distill oi! excess acetone- The. residue was under vacuum. 206.1 g. oi N-seconda'ry mty -flfv ny -p-pb w. at 90' to 95' C. at 0.1 to 0.2 mm. of mercury pressure were obtained. This yield or 99.5 per cent. 8.4 in the still pot as residue. I In a manner similar to that illustrated in the foregoing examples. other I N-aikyl-p-nitroanilines. e. g. N-methyl-pmitroaniiine. N-ethyibe reductiveiy alkylated using acefaline, methyl diethyl hetone, methyl n propyl ketone, methyl primary n-butyl ketone. methyl secondary butyl ketone. methyl isobutyl ketone. ketone or 'oi the hexanone can be used. in a manner similar to that uhistrated. amples, H-alkyl-p-nitroanilines can an aldehyde, such as I propionaidehyde, n-butyraidehyde. isobutyraidehyde or isomeric valdehydes. whenever aldehydes areto stages beyond the stituted phenylenediamines. unless is controlled by lowering the-temperatureand hydro en pressure, action when the required amount of hydrogen has been absorbed. This tendency for aikyiation to go beyond the di-substituted derivativesappears to be substantially absent when ketones are employed.

The phenylene amine derivatives accordance with our 'new I terioration of cracked gasoline when incorporated therein. However, the derivatives prealdehydes are practically no utility since they introduce very bad line. The derlvativu prepared other hand are remarkable mun: re p ct color in the g irom ketones on the Hydrogenation catalysts such asnaney nickel since to 1500 pounds per e boiling ketones. Acetophenone and cyclom process retard the" tie-f for 6% hours.

, aikyli -p-nheny1eneaiamine quantity represented a g. oi materialremained N-n-propyl-p-nitroaniline can inthe foregoinl exbe reducthe reaction so as to intercept the rein their presence appreciable hydrogenation of thebenzene ring- Ogthfi N-aikylp-nitroaniline takes. place. I

The N-secondary' but-yl-p-nitroaniline embe prepared by condensing p-chloronitrobenaene with secondary butyl amineginthe. presence or potassium rdichromate, in accordancewith the disclosure or our. copending application. Serial filed or even date herewith. i q

What we claim as our invention and desire to secure by Letters Patentoi the United States a" NJW-diaikyl-P- heny comprlsinl hydrogenatins a mixture ci a ii-aityi-p-nitroanilim and a comseiectedircm-the grcupeonsistingotaliphatic aldehydes and aliphaticketcnes. in the resence oi a ca comprising essentially an intimate mixture of copper oxide. chromium oxide and barium oxide.

l 2. A process ifor preparing a N.N'-diaikyi-pphenyienediamine 'ccmprisinl hydrogenatins a mixture oi a N-alUl -p-nitroaniline and an ali- -phaticketone.inthepresenceciacatalystcom- 0 tialiy an intimate mixture of copessen per oxide, chromium oxide and barium oxide.

(secmidby I 8. A process for preparing a N,N'-diting a mixture oi N-seeondary alkyl-p nitroa'niline and an aliphatic ketone, in the pres ence oi-a catalyst comprising essentially mate mixture oi copper oxide,

and bariumoxide.

a aikyD-p-ph l nediamim cent of the nitroanilinc temperatm'e oiirom about from about as otthe at a to about-1101c;

'ence of cent by weight r! b vl) ep-n en l n sm n hrdrogenating a' mixture oi. N-seconda'ry butyl-pnitroaniline and methylethyl keton'e,

en'ce oiirom about 0.5 per cent to aboutio per 8. A process' for preparing a EW-dldsedondjary butyD-p-phenylen I comprising hyose s. s, nitroaniline and methylethyl ketcne. in ence oifiromfabout 0.5' p'ercent to about-i0 per cent by weight oithe mixture'ot the nitroanilifl and ketone. or a catalystcomprisins essen an intimate mixture oi'copper oxide.

oxide and'barium oxide, at a abo'utiOO' toabout C. I I I a 0. A process for preparting a i m butyl -W-isopropyl-p-phenyl comprisins ting a mixture p-nitroaniline and in-the presence at a oxide.

we W n! oxide. 10.1 rocess for h ydroscnating a mixture or II -second!!! troanilin but!!- p-ni and in the irom-"aboutob per centfto about weight of the I lyst oemprisins eaten aninti- I i. Aprocessior preparing a luP-di-(seccndcomprisinl hy-Q lathe-preso! N -secondary buUi-p- N-aeocnda' bumai'i-secondal'y' I bu about 170C.

p-nitroaniline and acetone, in the presence of 5 enediamine.

from about 0.5 per cent to about 10 per cent by weight oi the nitroaniline and acetone.'of a cats- LEE G. DAVY.

lyst comprising essentially an intimate mixture CERTIFICATE OF CORRECTION.

Patent No. 2,581,015.

Angus t 7, 19145.

HAROLD VON BRAHER, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows; Page 1, first columm'line 13, strike out "a mixture of a N-a1kyl-' and insert instead --phenylenediamine or--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 13th day of November, A. D. 1915.

iSeal) Leslie Frazer First Assistant Commissioner oi Patents.

HAROLD VON BRAMER.

01' copper oxide, chromium oxide and barium oxide, at a temperature of from about 100 C. to

12. N-secondary butyl-N'-isopropyl-p-phenylabout 170C.

p-nitroaniline and acetone, in the presence of 5 enediamine.

from about 0.5 per cent to about 10 per cent by weight oi the nitroaniline and acetone.'of a cats- LEE G. DAVY.

lyst comprising essentially an intimate mixture CERTIFICATE OF CORRECTION.

Patent No. 2,581,015.

Angus t 7, 19145.

HAROLD VON BRAHER, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows; Page 1, first columm'line 13, strike out "a mixture of a N-a1kyl-' and insert instead --phenylenediamine or--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 13th day of November, A. D. 1915.

iSeal) Leslie Frazer First Assistant Commissioner oi Patents.

HAROLD VON BRAMER.

01' copper oxide, chromium oxide and barium oxide, at a temperature of from about 100 C. to

12. N-secondary butyl-N'-isopropyl-p-phenyl- 

